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Problem 1 - 23 Points: Part A
Problem 1 - 23 Points: Part A
PART A
1-1. Determine the molecular formula and write a balanced equation with correct state of
matters for the combustion of Q.
3 marks
2 marks for correct formula of Q.
1 mark for correct balanced equation with proper states.
1-2. Calculate the heat capacity of the calorimeter (excluding the water).
Calculation with proper units:
6 marks
Problem 1
Problem 1
PART B
3 marks
1-5. Calculate the freezing point (Tf) of a solution containing 0.244 g of Q in 5.85 g of
benzene at 1 atm.
Calculation
Tf of solution is 4.54 °C
6 marks
-1 mark for incorrect temperature.
-1 mark for incorrect heat of fusion.
1 mark
2-4. What are the amounts (mmol) of Na2A and NaHA initially present?
Calculation:
At pH 8.34 which is equal to (pKa1 + pKa2)/2 all A2- are protonated as HA—.
Therefore no. of A2- initially present in the solution = 0.300 x 10.00
= 3.00 mmol
At pH 10.33 , the system is a buffer in which the ratio of [A2-] and [HA—] is
equal to 1. Thus
[HA—] initial + [HA—] formed = [A2- ]initial - [HA— ]formed
The amount of initial HA— = 3.00 – 0.300 - 0.300 mmol = 2.40 mmol
____________ Problem 2
2-5. Calculate the total volume of HCl required to reach the second equivalence point.
Calculation:
____________ Problem 2
PART B
5 marks
Problem 2
2-7. Apart from H+, OH-, and H2O, what are all the chemical species present in the
solution resulting from mixing Solution II and Solution III at 1:1 volume ratio?
1.5 marks
2-8. What is the absorbance at 400 nm of the solution in (2-7) ?
Calculation:
When solutions II and III are mixed at 1:1 volume ratio, a buffer solution
of 0.05 M CH3COO- / 0.45 M CH3COOH is obtained.
[CH 3 COOH]
[H+] of mixture solution = Ka −
[CH 3COO ]
0.45
= 1.75 x 10-5 x
0.05
= 15.75 x 10-5 (1.0 mark)
[In − ] K
In
therefore =
[HIn] [H + ]
10 −3.38
=
15.75x10 −5
[In − ]
= 2.65 (1.0 mark)
[HIn]
Whereas [HIn] + [In-] = 10-5
[In − ]
+ [In-] = 10-5
2.65
[In-] = 0.726 x 10-5
(1.5 marks)
0.726 x10 −5
∴ Absorbance of solution = x 0.300
1.0x10 −5
= 0.218
(0.5 mark)
-0.5 mark for incorrect unit
Problem 2
2-9. What is the transmittance at 400 nm of the solution in (2-7)?
Calculation:
= 0.605
232
90 Th → 82 208
Pb + 6 42 He + 4β -
Energy released is Q value
Q = [m(232Th)-m(208Pb)-6m(4He)]c2
(the mass of 4e- are included in daughters) (2)
= [232.03805 u - 207.97664 u - 6 x 4.00260 u] x 931.5 MeVu-1
= (0.04581u)(931.5 MeVu-1) = 42.67 MeV (2)
4 marks
Problem 3
3-3. Calculate the rate of production of energy (power) in watts (1W = Js-1) produced by
1.00 kilogram of 232Th (t1/2 = 1.40 x 1010 years).
Calculation:
1000g x 6.022x1023atomsmol-1
1.00 kg contains =
232g mol-1
= 2.60 x 1024 atoms (1)
232
Decay constant for Th
0.693
λ = 10 (1)
x107s y−1)
(1.40x 10 y)(3.154
= 1.57 x 10-18 s-1
5 marks
Problem 3
3-4. What volume in cm3 of helium at 0 °C and 1 atm collected when 1.00 gram of 228Th
(t1/2 = 1.91 years) is stored in a container for 20.0 years.
Calculation:
208
228Th → Pb + 5 4He (1)
The half-lives of various intermediates are relatively short compared that
of 228Th.
23 −1
A = λN = ( 0.693)[(1.00g)(6.022X 10-1 mol )]
1.91y 228g mol
= 9.58 x 1020 y-1 (1)
Number of He collected
NHe = (9.58 x 1020 y-1)(20.0 y)(5 particles)
= 9.58 x 1022 particles of He (1)
1
(9.58x1022)(22.4
L mol−1)(103cm3L − )
VHe =
6.022x1023mol−1
= 3.56 x 103cm3 (2)
5 marks
3-5. One member of thorium series, after isolation, is found to contain 1.50 x 1010
atoms of the nuclide and decays at the rate of 3440 disintegrations per minute.
What is the half-life in years?
Calculation:
A = λN;
0.693 0.693N
t1/2 = = (1.5)
λ A
50 x1010 atoms)
(0.693)(1.
= (1.5)
3440atomsmin-1
= 3.02 x 106 min
= 5.75 years (1)
4 marks
Problem 4 28 points
Knowing that L was synthesized from bipyridine and during the reaction
bipyridine was simply oxidized to bipyridine oxide. The molecular mass
of bipyridine is 156 (for C10 H8 N2) while the molecular mass of L is 188.
The difference of 32 is due to 2 atoms of oxygen. Therefore , the
molecular formula of L is C10H8N2O2.
or or
N N N+ +N N N
N N
O O O- -O O O
Structure of bipyridine
structure of L
2 marks 2 marks
4-3. Does the ligand L have any charge, i.e., net charge ? (Please tick).
√
1 mark
4-4. Draw the structure when one molecule of L binds to metal ion (M).
N N
O O
M
2 marks
Problem 4
Fe C H Cl N O
% 5.740 37.030 3.090 10.940 8.640 34.560*
mol 0.103 3.085 3.090 0.309 0.617 2.160
mol ratio 1.000 29.959 30.00 2.996 5.992 20.971
atom ratio 1 30 30 3 6 21
( * Percentage of O is obtained by difference.)
3 marks
What are the values of m and n in FeLm(ClO4)n.3H2O?
m = 3 n = 3
1 mark 1 mark
Since the molecular formula contains one atom of Fe , so in this case the
empirical formula is equivalent to the molecular formula. The molecular
formula of L has been obtained previously in (4a) and (4b) , therefore
we can work to find m = 3. Having obtained the value of m , one can work
out for n and find that n = 3.
1 mark
The ratio of cation to anion is 1 : 3 1 mark
Problem 4
eg
eg
t2g t2g
Low spin configuration
High spin configuration
2 marks
Which configuration , high or low spin , is the correct one (please tick)?
√ High spin
Low spin
1 mark
Problem 4
The best evidence to support your answer for this high/low spin selection:
Color
√ Magnetic moment
Molar conductance
1 mark
We can use a simple relation between number of unpaired electrons and the
magnetic moment as follows.
ì = n(n + 2)
1 mark
Problem 4
From ì = n(n + 2)
1 mark
x = 2 1 mark
y = 2 1 mark
z = 1 1 mark
Problem 5 23 points
5-1. Write structures of A - D with appropriate stereochemistry in Haworth projection,
except for B.
CH2OH
O CH 2
OH OO CH CN HO CH CN
OH
OH
OH OH
OH
A B
(3 marks) (1 mark)
Remark: 1 for cyanohydrin moiety, 1 for two D-glucose units
and 1 for 1,6-linkage
CH 2OH CH2OH
O CH2 OH(H)
OH O OH(H) OH
OH H(OH)
OH OH
OH OH H(OH) OH
OH
C D
(2 marks) (1.5 marks)
Remark: 1 for two glucose units Remark: 0.5 for correct structure
0.5 for 1,6-linkage 1 for stereochemistry
0.5 for β-linkage
5-2. Write molecular formula each for compounds F and G and structural formula for
compound H and I and indicate stereochemistry of H.
HOOC
Molecular formula of COOH
NH
compound F = HCN NH
S
Problem 5
5-3. Deduce the absolute configuration of (-) E and the structure with configuration of
each intermediate (J-O) in the sequence with the proper R,S-assignment.
SN1
√ SN2
SNi
E1
E2
1 mark
Problem 6 16 points
6-1.
2 sulfonic acid groups are formed from oxidation of a disulfide bond.
1 mark
6-2. Complete structure of DNP-Asp at its isoelectric point is
O
O2N
OH
OH
N
NO2 H O
2 marks
Remarks
2 marks for exactly the same structure
-1 mark for the condensed structure
-0.5 mark for Zwitterionic form
0 mark for misplaced DNP group
6-3.
The sequence of B8 is Cya-Tyr-Ile-Glu
2 marks
Remarks
-0.5 marks if the sequence is correct but the symbol "Cys" is used in place of "Cya"
-1 mark if "Cya" is put correctly at N-terminus but the sequence is incorrect
0 mark for the reverse sequence
6-4.
The sequence of B9 is Asp-Cya-Pro-Leu
1 mark
Remarks
-0.5 marks if the sequence is correct but the symbol "Cys" is used in place of "Cya"
0 mark for wrong sequence even if Asp and Leu are placed correctly since the
information is already provided in the question
Problem 6
Cys-Tyr-Ile-Glu-Asp-Cys-Pro-Leu-Gly-NH2
5 marks
Remarks
5 marks for exactly the same sequence with correct placement of disulfide bond
- 1 mark for missing or misplaced the disulfide bond.
- 0.5 marks for missing "NH2" group at C-terminus.
- 0.5 for using the symbol "Cya" is used in place of "Cys".
0 mark if the sequence wrong.
6-6. Write the revised structure of A below and circle the site(s) to indicate all the possible
source of ammonia
3 marks
Remarks
0.5 marks for each correct position of the amide group (Glu->Gln, Asp->Asn and at C-
terminus)
0.5 marks for each circle at appropriate places (circle at Gly is allowed)
6-7.
The isoelectric point of A is 9
2 marks